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The use of nitriding to enhance wear resistance of cast irons

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DOI: 10.2495/SECM130141

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 Surface Effects and Contact Mechanics XI 171

The use of nitriding to enhance wear resistance

of cast irons
Z. Yang1, D. O. Northwood1, X. Sun2, R. Lumbreras3,
G. C. Barber3 & Q. Zou3
1
Mechanical, Automotive and Materials Engineering,
University of Windsor, Canada
2
Chrysler LLC Tech Center, USA
3
Mechanical Engineering, Oakland University, USA

Abstract
This research is focused on using nitriding to enhance the wear resistance of
austempered ductile iron (ADI), ductile iron (DI), and gray iron (GI). Three gas
nitriding processes, namely “Gas nitriding + nitrogen cooled down to 800oF”
(Blue), “Gas nitriding + cooled down to 300oF” (Gray), and “Gas nitriding + oil
quenched” (Oil) were used. This study was carried out through optical
metallography, roughness measurements, microhardness, and SEM. The ball-on-
disc wear tests were conducted under lubricated conditions. It was found that
COF for all materials in all nitrided conditions was small (<0.045). The best
wear performance was seen for ADI processed using the Gray and Oil gas
nitriding processes. These processes produced a compound layer thickness of 4–
6μm, a low surface roughness (0.8–1.3 μm, Ra) and a high surface
microhardness (1800–2200 HV). The wear rate decreased with increasing
surface microhardness and decreasing surface roughness.
Keywords: cast irons, ADI, DI, GI, nitriding, wear.

1 Introduction
Cast irons have played an important role in human history. They are ferrous
alloys with carbon contents higher than 2.1%, silicon and often other alloying
elements. Generally, they are divided into the following basic types: White Iron,
Gray Iron, Ductile Iron, and Malleable Iron [1]. They are widely used in the

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172 Surface Effects and Contact Mechanics XI

automotive industry for applications such as fly-wheels, cylinders, camshafts,

gears, and rolls [2–4].
Nitriding is one of the most popular methods for surface engineering. It is a
low-temperature heat treating process that diffuses nitrogen into the surface of a
metal to create a hardened surface. Nitriding is predominantly used on steel, but
also cast irons, aluminum and titanium. Nitrided steels are widely used due to
their superior hardness and attractive surface hardness, fatigue life, and
tribological properties [5].
Wear is one of the major forms of material deterioration, often limiting both
the life and the performance of the industrial components and requiring frequent
replacement of the components. Wear is affected by a variety of conditions, such
as the type of lubrication, loading, speed, temperature, materials, surface finish,
and hardness. Wear types include adhesive wear, abrasive wear, surface fatigue,
fretting wear, erosive wear, and corrosive wear. It may be difficult to recognize
the various damages types. However one type of damage is usually predominant
[4–7].
Because the surface properties of cast irons do not match the performance
requirements of the automotive industry, research is required to improve the
surface properties of these materials, especially the wear resistance.
Three gas nitriding processes were used for the cast irons. All nitrided
materials were examined using optical metallography, profilometry and
microhardness to determine the nitrided case microstructure, surface roughness
and through-thickness microhardness. Wear testing was performed for all
nitrided cast irons using a ball (ceramic)-on-disc apparatus under lubricated
conditions.

2 Experimental details
In the present research, austempered ductile iron (ADI), ductile iron (DI), and
gray iron (GI) were treated using “Gas nitriding + nitrogen cooled down to
800oF” (Blue), “Gas nitriding + cooled down to 300oF” (Gray), and “Gas
nitriding + oil quenched” (Oil). After the samples were nitrided, the nitrided
layer was characterized using optical microscopy, Vickers microhardness testing,
and SEM.
Samples for optical metallography were prepared according to ASTM E768-
99(2010) [8]. All sections examined were cross-sections perpendicular to the
large flat nitrided surface. A CSM Micro-Hardness Tester (MHT) was used to
measure the microhardness of the compound layer and diffusion zone. The load
used was 0.025N. The measurements were carried out according to ASTM
E384-11 [9]. Surface topographies of the nitrided surface layer were
characterized by a two-dimensional profilometry tester (Mitutoyo SJ201),
according to ASTM B946-11 [10].
For every material/nitriding combination, wear tests were done using a ball-
on-disc test apparatus according to ASTM G190-06 [11] and ASTM G133-
05(2010) [12] standards. They were carried out under lubricated conditions with
a constant load of 10 lb for 1 hour. The rotation speed was constant, 1.67m/s

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 Surface Effects and Contact Mechanics XI 173

(700 rpm, wear track radius 22.75mm). The lubricant was light mineral oil. The
coefficient of friction (COF) was recorded during the test. As the counterface in
the wear test, the properties of ceramic ball are: nonporous high-alumina ceramic
ball; Diameter: 5/16"; Hardness: 1700 Vickers. It should be emphasized that a
“new” ceramic ball was used for each wear test.
A FEI Quanta 200 FEG SEM equipped with an EDS system was used to
characterize the wear track and debris and to help identity the wear mechanisms.
The wear performance was related to the nitride layer parameters.

3 Experimental results and analysis

In this section, results are presented for the microstructure of the cast irons,
measurements of the compound layer thickness and diffusion zone depth, surface
roughness, surface and through thickness microhardness of the nitrided layer and
diffusion zone, and wear testing and characterization of worn materials. The
wear performance is then correlated to the microstructure and mechanical
properties.

3.1 Metallography of core material of cast irons

Optical micrographs of the core materials are shown in Figures 1(a)–(c). The
microstructure of DI, Figure 1(a), primarily consists of a pearlite matrix and
graphite nodules with surrounding ferrite (white phase). The microstructure of
ADI, Figures 1(b), consists of an ausferrite matrix and graphite nodules. The
microstructure of GI, Figure 1(c) consists of a pearlite matrix and graphite flakes.

(a) Microstructure of DI (b) Microstructure of ADI (c) Microstructure of GI

Figure 1: Microstructure of DI, ADI and GI.

3.2 Metallography of nitrided layer

Optical micrographs of the three cast iron samples treated using the three gas
nitriding processes are presented in Figures 2–4 The microstructure of the
nitrided case is composed of a thin compound layer (CL) with a diffusion zone
(DZ) underneath. Good wear resistance is usually ascribed to this compound
layer and the hardened diffusion zone [13].
The nitrided layers on DI (Figure 2), are relatively thin with little variability
in thickness. The nitrided layers on ADI (Figures 3), show more variability in

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174 Surface Effects and Contact Mechanics XI

thickness. ADI treated using the Gray process is the thickest. In DI and ADI, the
compound layers could enclose the graphite nodules. The morphology of the CL
of GI is different from that for DI and ADI. For GI treated by either the Blue or
Gray processes, the incorporation of the graphite flakes into the compound layer
produces a very uneven surface (Figure 4).

Figure 2: Microstructures of DI treated by Blue, Gray and Oil processes.

Figure 3: Microstructures of ADI treated by Blue, Gray and Oil processes.

Figure 4: Microstructures of GI treated by Blue, Gray and Oil processes.

3.3 Compound layer (CL) thickness and diffusion zone (DZ) depth

Figures 5 and 6 present the results of the CL thickness and the DZ depth
measurements, respectively. From Figure 5, it can be seen that GI processed
using Gray nitriding has thickest compound layer, while ADI processed using

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 Surface Effects and Contact Mechanics XI 175

Blue nitriding has the thinnest compound layer. In general, the greatest
variability in CL thickness was shown by GI.
From Figure 6, it can be seen that the diffusion zone depth is largest for GI,
which is same trend as for the compound layer. ADI generally has the smallest
diffusion zone depth. Thus, the nitriding process that produced the highest
compound layer thickness also produces larger diffusion zone depths.
Comparing the nitriding processes, Gray produced the thickest compound
layer, followed by Blue, and then Oil. GI has the thickest compound layer on
average, but the greatest variability in thickness. The Oil quench from gas
nitriding produced the thinnest compound layer, and DI has thinnest compound
layer. Gray gave the highest diffusion zone depth. GI has the highest DZ depth
and ADI has the lowest DZ depth.

20 250
CL thickness (μm)

16 DZ depth (μm) 200
12 150
8 100
4 50
0 0
GRAY

GRAY

GRAY
BLUE

OIL

BLUE

OIL

BLUE

OIL
GRAY
OIL

GRAY
OIL

GRAY
OIL
BLUE

BLUE

BLUE

DI(CL) ADI(CL) GI(CL) DI ADI GI

Figure 5: Compound Layer thickness. Figure 6: Diffusion Zone depth.

3.4 Microhardness

The microhardness measurements are presented in two sections, namely nitrided

layer surface hardness and cross-sectional hardness. Measuring the
microhardness of the nitrided layer is not an easy task because the thickness of
the layer is of comparable dimensions to the indenter. The hardness is also
influenced by the specific surface topography and graphite (soft phase) content
in the area of the indent. The highest measured values are given in Table 1.

Table 1: Maximum values for surface microhardness of nitrided cast irons.

DI ADI GI
BLUE GRAY OIL BLUE GRAY OIL BLUE GRAY OIL
HV 2071 1913 2136 1767 1879 2251 1072 1017 1612

The highest microhardness (2251HV) was measured for ADI treated using
Oil quenching after gas nitriding. However, ADI treated using Blue and Gray
processes and DI treated using Blue, Gray and Oil processes, have a high
microhardness (2000±250HV). These high hardness levels should result in better

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176 Surface Effects and Contact Mechanics XI

wear performance. However, the microhardness for GI, no matter what nitriding
treatment was applied, is very much lower, i.e. around 1000HV, except for the
Oil quench processing. This lower hardness is attributed to the graphite flakes
which are incorporated into the compound layer (see for example Figure 4).
Figures 7(a)–(c) show the through-thickness microhardness measurements for
DI, ADI, GI as plotted using Origin Pro software. A similar microhardness
gradient is seen for all materials in all heat treated conditions. The
microhardness of the compound layer is not reflected in these plots but rather the
nitrogen distributions in the diffusion zone.

1600 1200
ADI GI
1400 DI
BLUE 1100 GI-BLUE
BLUE GRAY GI-GRAY
GRAY 1400
1200 OIL 1000 GI-OIL
OIL
(a) (b) (c)
Microhardness

1200 900
Microhardness

Microharness
1000
800
800 1000
700

600 800 600

500
400 600
400
0 100 200 300 400 500 0 100 200 300 400
0 50 100 150 200 250 300
Distance(μm) Distance(μm) Distance(μm)

Figure 7: Microhardness of cross-sections.

3.5 Surface roughness

From the surface roughness results plotted in Figure 8, it can be seen that ADI
treated using the Oil nitriding has lowest surface roughness, while GI treated
using the Blue process has the highest surface roughness. GI treated using the
Gray nitriding process showed the highest variability in roughness and a
relatively high roughness value. In general, it can be seen that ADI has the
lowest surface roughness.

Figure 8: Surface roughness (Ra: μm) after nitriding.

3.6 Wear track width and depth measurements

Good tribological properties of nitrided materials are usually ascribed to the

compound layer. To characterize the enhancement of wear resistance derived
from the nitriding treatments, one of the simplest, but effective, methods is to
measure the dimensions (width and depth) of the wear track. The width and
depth of the wear tracks measured using a combination of SEM and image

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 Surface Effects and Contact Mechanics XI 177

analysis software (Image J), are given in Figure 9 for wear track width (WTW),
and Figure 10 for wear track depth (WTD). Given that the counterface is a
ceramic ball, the wear track width increases as wear proceeds, i.e. as the ceramic
ball penetrates the nitride layer. Figure 9 shows that ADI processed using Oil
quench nitriding has the best wear resistance, while GI processed using Gray
nitriding has the worst wear resistance. DI processed using Gray and Oil
nitriding process has better wear resistance, compared with DI processed using
Blue. ADI, regardless of nitriding treatment has better wear resistance. The wear
track depth results (Figure 10), lead one to similar conclusions.
We can see that the Oil nitriding process gave the best wear resistance of the
three cast irons, and nitrided ADI exhibited the best performance.

Figure 9: Wear track width. Figure 10: Wear track depth.

3.6.1 Comparison of wear track depth with CL thickness and DZ depth

In order to investigate whether the compound layer are still protective after the
wear test, and to know how much of the nitrided layer has been worn away, the
wear track widths have been compared with the CL thickness and DZ depth. It
was found that wear track depths are close to the values of the CL thickness, but
are smaller than DZ depth. The difference between the CL thickness and wear
track depth is given in Figure 11. For the duration of the wear test, the compound

Figure 11: The difference between the CL thickness and wear track depth.

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178 Surface Effects and Contact Mechanics XI

layers on ADI nitrided using either the Gray or Oil nitriding process was still
protective. For all other material/nitriding process combinations, the CL was
completely worn away. Thus the wear protection mechanisms switch from CL
protection to DZ protection.

3.7 Coefficient of friction (COF)

The coefficient of friction was recorded continuously during the wear test. It
is mainly related to the surface roughness, compound layer parameters and
the lubricated condition. As shown in Figures 12(a)–(b), the COF is always
less than 0.045 indicating lubricated conditions. The COF either increased
during the wear test because debris with hard particles accumulated in the
wear track, e.g. DI-Gray, or decreased because the wear track was polished
by the counterface ceramic ball and there was little or no debris.
DI-Blue
DI-Grey DI-Blue-STD
0.05 0.018 DI-Grey-STD
DI-Oil
ADI-Blue DI-Oil-STD
0.016 ADI-Blue-STD
ADI-Grey
ADI-Oil ADI-Grey-STD
0.04 0.014
GI-Blue ADI-Oil-STD
GI-Grey 0.012 GI-Blue-STD
GI-Oil GI-Grey-STD
0.03
COF-STD

GI-Oil-STD
COF-AVE

0.010
0.008
0.02
0.006

0.01
0.004
0.002
0.00 0.000
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Time(min) Time(min)

(a) COF (average) of cast irons (b) The variability of the COF of cast irons

Figure 12: Coefficient of friction VS time plots for nitrided cast irons.

3.8 SEM observations of wear tracks

SEM was used to characterize the wear track morphology and debris to help
identity the wear mechanisms. Figures 13(a)–(c) for DI indicate that all tracks
look polished. Figures 14(a)–(c) for ADI indicate that wear tracks also look
polished, but there is less debris than for DI. New pits were not as easily formed
as in DI, but some pits still formed at the graphite nodules. Figures 15(a)–(c) for
GI show the polished tracks. The amount of debris is more than that for DI or
ADI. New pits are more easily formed at graphite flakes. Fewer pits were found
for the oil quenched sample. This is consistent with the coefficient of friction
(COF) data for GI (Figure 12), where the COF for GI-Blue and GI-Gray increase
with time/sliding distance whereas GI-Oil shows a small decrease in COF with
time. Wear mechanisms for these tests are predominantly adhesive wear,
whereas abrasive wear could occur when debris accumulated.

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 Surface Effects and Contact Mechanics XI 179

(a) (b) (c)

Figure 13: Wear track morphology as measured using SEM for (a) DI-Blue,
(b) DI- Gray and (c) DI- Oil.

(a) (b) (c)

Figure 14: Wear track morphology as measured using SEM for (a) ADI-Blue,
(b) ADI- Gray and (c) ADI- Oil.

(a) (b) (c)

Figure 15: Wear track morphology as measured using SEM for (a) GI-Blue,
(b) GI- Gray and (c) GI- Oil.

3.9 Wear rate

Wear rate is commonly calculated using two main formulas, based either on
weight loss [14] or volume loss [15] k= ΔV/FS (eqn. (1)), where k is the wear
rate coefficient, ΔV wear volume loss, F the normal load, and S the total sliding
distance. The second is more widely used and more applicable to this study
because of the different densities of the materials used in this study. In this study:

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180 Surface Effects and Contact Mechanics XI

Figure 16: Average wear rate of the nitrided cast irons.

F=44.45N (10lbs); S=6003.58m; FS=266871.6Nm. The calculated wear rates of

the nitrided cast irons and Isonited 4140 steel are shown in Figure 16.
ADI treated using Oil nitriding process has the lowest wear rate. This is
attributed to the optimum CL thickness, CL morphology, the adherence of the
compound layer to the substrate, high hardness, and low surface roughness. GI
treated using Gray nitriding process has the highest wear rate. Although the
compound layer is thicker, it is softer and less adherent and has a higher surface
roughness. The properties of the CL on ADI (Oil) and GI (Gray) are compared in
Table 2.

Table 2: Comparison of ADI (Oil), the best wear resistance, with GI (Gray),
the poorest wear resistance.

ADI (Oil) GI (Gray)

Compound Layer Thickness ~5μm, little variability ~12μm, large variability
Morphology CL could incorporate Graphite flakes
graphite nodules incorporated into CL
Adherent Yes Partially
Max. Surface Hardness(HV) 2251 1017
Surface Roughness (μm) 0.93±0.13 2.03±0.60
COF 0.025-0.03 0.04

The relationship between wear rate and roughness and microhardness of

nitrided surface are shown in Figures 17 and 18. The linear fitting functions of
wear rate against roughness and microhardness of nitrided surface are given in
Equations (2) and (3). For Equation (2), the Residual Sum of Squares (RSS) is
7.27864-12, which indicates good linear relationship between wear rate and
roughness. For Equation (3), the Residual Sum of Squares (RSS) is 3.5673-12,
which also indicates good linear relationship between wear rate and
microhardness.

Wear rate(10-6mm3/Nm)= 1.79Ra -1.00 (2)

Wear rate(10-6mm3/Nm)= 6.14-0.0024HV (3)

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 Surface Effects and Contact Mechanics XI 181

(1.0 mm /Nm)
5 GI-Gray
3

(1.0 mm /Nm)
5 GI-Gray
4
-6

3
4

-6
3 GI-Blue
DI-Blue 3 GI-Blue
Wear rate

GI-Oil DI-Blue

Wear rate
2 DI-Gray
ADI-Blue 2 GI-Oil
ADI-Gray DI-Gray
DI-Oil ADI-Blue
ADI-Gray DI-Oil
1
1
ADI-Oil
ADI-Oil
0 0

0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 1000 1200 1400 1600 1800 2000 2200 2400
Roughness (Ra: μm) Microhardness (HV)

Figure 17: Function of wear rate Figure 18: Function of wear rate
against surface roughness. against microhardness
of nitrided surface.

4 Conclusions
The main conclusions were:

1. The COF for all cast irons in all nitrided conditions was small (<0.045),
reflecting the lubricated test conditions (fully flooded or starved lubrication).
2. Small differences were seen in the variation of COF with time. A very small
decrease in COF with time is interpreted as being related to polishing of the
wear track. A small increase in COF with time is thought to be related to
accumulation of debris in the wear track. When the COF stays essentially
constant with time, it is considered that the polishing of the wear track is
“balanced” by accumulation of some debris.
3. The overall wear rate is shown to be primarily dependent on two parameters,
namely the surface roughness and surface microhardness of the nitrided
material. The wear rate decreased with increasing surface microhardness and
decreasing surface roughness.
4. The best wear performance is shown when the wear track does not fully
penetrate the compound layer. Such behaviour was seen for ADI processed
using the Gray and Oil nitriding processes. These processes produced a
compound layer thickness of 4-6μm, a low surface roughness (0.8-1.3 μm,
Ra) and a high surface microhardness (1800-2200 HV) reflecting a dense and
adherent compound layer. The compound layer thickness in GI was larger
(up to 12μm) but it was not as hard (1000-1500 HV) and the roughness was
higher (up to 2.5μm, Ra) and showed the greatest variability.

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